Hydrocarbon conversion process using a pillared clay containing fluorided pillars

ABSTRACT

Hydrocarbon conversion processes are disclosed which are catalyzed by novel pillared clay compositions. The clay contains pillars which are at least partially fluorided. These pillars are metal fluoro hydroxy cations where the metal can be Al, Zr, Si/Al, Ti or Cr. The clays which can be pillared with these pillars are the smectite clays which include hectorite and beidellite along with synthetically prepared smectite clays. These clays are prepared by pillaring the clay, followed by calcination and then treatment with a fluoride salt such as ammonium bifluoride.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of prior copendingapplication U.S. Ser. No. 08/133,939 filed on Oct. 12, 1993 which isincorporated by reference.

FIELD OF THE INVENTION

This invention relates to a hydrocarbon conversion process using apillared clay composition in which the pillars are fluorided pillars.The clay is any of the smectite class of clays such as hectorite orbeidellite.

BACKGROUND OF THE INVENTION

Clays are composed of infinite layers (lamellae) of metal oxides andhydroxides stacked one on top of the other. These layers or sheets arecomposed of tetrahedrally coordinated cations which are linked throughshared oxygens to sheets of cations octahedrally coordinated to oxygensand hydroxyls. When one octahedral sheet is linked to one tetrahedralsheet a 1:1 layered structure is formed as in kaolinite, whereas whenone octahedral sheet is linked to two tetrahedral sheets, a 2:1 layeredstructure is produced as in beidellite. Anionic charges on thetetrahedral layers (usually siliceous layers) are neutralized by cationssuch as Na⁺ or Ca⁺² in the interlamellar spaces. These cations can beexchanged with other cations.

Some of the clays are swellable, i.e., they swell or expand when placedin water or other solvents. These clays include the smectite group ofclays which are 2:1 layered clays. Included in the smectite group aremontmorillonite, beidellite, nontronite, hectorite, saponite, Laponite™,and sauconite. The clay layers in these swellable clays can be proppedopen or pillared with large cations such as Fe⁺³, Cr⁺³ or with metalhydroxy polymer cations such as (Al₁₃ O₄ (OH)₂₄ (H₂ O)₁₂)⁺⁷ or(Zr(OH)₂.4H₂ O₄ ⁺⁸.

Pillared clays are known to catalyze numerous reactions such asalkylation, cracking, ester formation, dimerization, oligomerization,etc. A review of the reactions catalyzed by pillared clays may be foundin an article by J. M. Adams, Applied Clay Science, 2, pp. 309-342(1987). Of these reactions, alkylation has received considerableattention. For example, U.S. Pat. No. 4,499,319 discloses layered clayssuch as montmorillonite which have been ion-exchanged with metal cationssuch as chromium and aluminum, which are used to alkylate aromaticcompounds. Other examples include U.S. Pat. No. 4,605,806 whichdiscloses a hydrogen ion-exchanged pillared clay; U.S. Pat. No.3,965,043 discloses a metallic cation exchanged trioctahedral 2:1layer-lattice smectite-type clay and U.S. Pat. No. 3,979,331 whichdiscloses a metallic cation exchanged synthetic hectorite-type clayuseful for alkylating aromatic hydrocarbons.

It is also reported that the swellable clays can be fluorided and thenpillared. For example, Butruille et al. in J. of Catalysis, 139, 664-678(1993) disclose synthesizing a fluorided hectorite clay which is thenpillared with an Al₁₃ polycation and subsequently calcined. The authorsreport enhanced catalytic activity for propylene alkylation relative tononfluorinated smectite hosts.

In contrast to this art, applicant has prepared a pillared smectite clayin which the pillars have been fluorided. For example, a montmorilloniteclay was pillared with aluminum chlorohydrate (ACH), calcined and thentreated with a fluoride salt such as ammonium fluorosilicate. Activitytesting shows that the fluorided pillared clay of this invention hasenhanced activity versus a fluorided clay that has been pillared.

SUMMARY OF THE INVENTION

As stated, this invention relates to a hydrocarbon conversion processusing a pillared clay in which the pillars have been fluorided.Accordingly, one embodiment of the invention is a hydrocarbon conversionprocess comprising contacting a hydrocarbon feed under hydrocarbonconversion conditions with a catalyst to give a hydroconverted product,the catalyst comprising a smectite clay having the empirical formula

    A.sup.n.sub.(x+z/n) (M.sub.8-x M1.sub.x)(M2.sub.(y-z) M3.sub.z)O.sub.20 (OH).sub.4

where A is a counter ion selected from the group consisting of alkalimetals, alkaline earth metals, secondary amines, tertiary amines,quaternary ammonium cations and quaternary phosphonium cations, n is thecharge on said counter ion, M is silicon or germanium, M1 is a metalhaving a +3 oxidation state selected from the group consisting ofaluminum, gallium, iron and chromium, x ranges from about 0 to about1.8, M2 is a metal having a +3 or a +2 oxidation state, M3 is a metalhaving a +2 or a +1 oxidation state, y is 4 when M2 is a +3 metal or 6when M2 is a +2 metal and z varies from about 0 to about 1.8, thesmectite clay having between its layers pillars which are metal fluorohydroxy polymer cations.

This and other objects and embodiments will become more apparent after amore detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

One essential element of the instant invention is a swellable clay. Theswellable clays are the smectite clays (natural and synthetic) whichinclude hectorite, beidellite, Laponite™, nontronite, saponite,sauconite and montmorillonite. These clays are represented by theempirical formula

    A.sup.n.sub.(x+z/n) (M.sub.8-x M1.sub.x)(M2.sub.(y-z) M3.sub.z)O.sub.20 (OH).sub.4

where A is a counter ion selected from the group consisting of alkalimetals, alkaline earth metals, secondary amines, tertiary amines,quaternary ammonium cations and quaternary phosphonium cations, n is thecharge on said counter ion, M is silicon or germanium, M1 is a metalhaving a +3 oxidation state selected from the group consisting ofaluminum, gallium, iron and chromium, x ranges from about 0 to about1.8. When M2 is a +3 metal it is selected from aluminum, gallium, ironand mixtures thereof. When M2 is a +2 metal, it is selected frommagnesium, zinc, nickel and mixtures thereof. The M3 metal is selectedfrom the group consisting of magnesium, zinc and lithium. The specificformulas for the various smectite clays are presented in Table 1.

                  TABLE 1                                                         ______________________________________                                        Formulas of Smectite Clays                                                    Clay Name        Formula                                                      ______________________________________                                        montmorillonite  A.sub.x Si.sub.8 (Al.sub.4-x Mg.sub.x)O.sub.20 (OH).sub.4                     1                                                            beidellite       A.sub.x (Si.sub.8-x Al.sub.x)(Al.sub.4)O.sub.20 (OH).sub.                     4                                                            nontronite       A.sub.x (Si.sub.8-x Fe.sub.x)(Fe.sub.4)O.sub.20 (OH).sub.                     4                                                            hectorite        A.sub.x (Si.sub.8)(Mg.sub.6-x Li.sub.x)O.sub.20 (OH).sub.                     4                                                            saponite         A.sub.x (Si.sub.8-x Al.sub.x)(Mg.sub.6)O.sub.20 (OH).sub.                     4                                                            sauconite        A.sub.x (Si.sub.8-x Al.sub.x)(Zn.sub.6)O.sub.20 (OH).sub.                     4                                                            Laponite ™    A.sub.x Si.sub.8 (Mg.sub.6-x Li.sub.x)O.sub.20 (OH).sub.4    SMC-1            A.sub.x (Ge.sub.8-x Al.sub.x)Al.sub.4 O.sub.20 (OH).sub.4    SMC-2            A.sub.x (Si.sub.8-x Ga.sub.x)(Ga.sub.4)O.sub.20 (OH).sub.                     4                                                            ______________________________________                                         The value of x varies from about 0.2 to about 1.8.                       

These clays either occur naturally or can be synthesized. Usually thesmectite clays are hydrothermally synthesized from a reaction mixturecontaining the required molar amounts of the desired metals. Thereaction mixture contains reactive sources of the desired metals such assodium aluminate, aluminum hydroxide, boehmite alumina, gibbsitealumina, aluminum isopropoxide, aluminum t-butoxide, colloidal silica,tetraethylorthosilicate (TEOS), tetramethylorthosilicate, galliumhydroxide, gallium chloride, gallium nitrate, germanium tetrachloride,germanium ethoxide, magnesium sulfate, magnesium fluoride, lithiumfluoride, iron chloride, chromium chloride, zinc sulfate and zincchloride. The counter ion is added as a salt or compound. Examples ofthe metal salts are sodium hydroxide, lithium hydroxide, potassiumhydroxide, cesium hydroxide and calcium hydroxide. Examples ofquaternary compounds are the hydroxide, chloride, iodide, bromide andcarbonite salts of the following cations: tetramethylammonium;tetraethylammonium; tetrapropylammonium; tetrabutylammonium;tetra-t-butylammonium; tetrapentylammonium; tetraphenylammonium.;tetramethylphos-phonium; tetraethylphosphonium; tetrapropylphosphoniumand tetraphenylphosphonium. Illustrative of the secondary and tertiaryamines which can be used are di-n-propylamine, ethylbutylamine,tripropylamine, triethylamine, piperidine, 2-methylpyridine,di-n-pentylamine, choline and N'N-dimethylbenzylamine. The pH of thereaction mixture can range from about 5 to about 14 and the mixturereacted at a temperature of about 50° C. to about 250° C. underautogenous pressure for a time of about 2 hours to about 21 days tocrystallize the desired clay.

Another necessary element of the instant invention is a metal hydroxypolymer cation which acts as a pillar to prop up the clay layers. Thepreparation of these metal hydroxy polymers is well known in the art.For example, one well known pillar is aluminum chlorohydrate (also knownas aluminum chlorohydroxide), ACH, which is a polymeric aluminum complexhaving the empirical formula

    Al.sub.2+n (OH).sub.2n Cl.sub.6

where n has a value of about 4 to 12. The preparation of this aluminumpolymer is generally known to those skilled in the art. See, forexample: Tsuitida and Kobayashi, J. Chem. Soc. Japan (Pure Chem. Sect.),64, 1268 (1943). Inoue, Osugi and Kanaji, J. Chem. Soc. Japan (Ind.Chem. Sec.), 61, 407 (1958).

The ACH pillar can be modified to include one or more rare earthelements such as cerium, lanthanum, neodymium, europium, etc. Thepreparation of these rare earth modified ACH pillars is described inU.S. Pat. No. 4,952,544 which is incorporated by reference. Basically,the ACH polymer is modified with the rare earth by adding a soluble rareearth salt, preferably a water soluble rare earth salt. Examples of rareearth salts are the nitrates, halides, sulfates and acetates. Preferredrare earth elements are cerium and lanthanum with cerium nitrate andlanthanum nitrate being the preferred salts. The rare earth isintroduced into the polymer or oligomer structure by mixing the rareearth salt either in solution (water preferred) or as a solid with theACH. The mixture is refluxed at a temperature of about 105° to about145° C. for a time of about 24 to about 100 hours. The weight ratio ofrare earth (expressed as oxide, e.g., CeO₂) to alumina (Al₂ O₃) in thesolution prior to refluxing is from about 1:52 to about 1:1.

Examples of other pillars are polymers or oligomers of zirconium,chromium, titanium, silicon and silicon/aluminum. Descriptions ofoligomers or polymers of these pillaring materials can be found in thefollowing references: 1) Si/Al--U.S. Pat. No. 4,176,090; 2)zirconia--Clays and Clay Minerals, 27, 119 (1979) and U.S. Pat. No.4,176,090; 3) titania--U.S. Pat. No. 4,176,090; 4) chromium oxide--U.S.Pat. No. 4,216,188 and 5) silicon oxide--U.S. Pat. No. 4,367,163, all ofwhich are incorporated by reference.

Having obtained the desired clay and pillar or pillar precursor, theclay is now pillared by means well known in the art such as described inU.S. Pat. No. 4,950,544 which is incorporated by reference. Usually theclay is added to a solution containing the pillar, stirred, filtered,redispersed with water (one or more times), isolated, dried and calcinedat about 300° C. to about 800° C. for a time sufficient to fix thepillars, usually from about 30 minutes to about 12 hours.

The pillars of the clay are now fluorided by treating the pillared claywith a solution of a fluoride compound. Examples of fluoride compoundsinclude ammonium fluorosilicate, ammonium bifluoride and ammoniumfluoride. The fluoriding process involves taking the calcined pillaredclay and dispersing it in water to form a slurry. To this slurry, thereis added a solution (aqueous) of the desired fluoride compound. Thefluoride containing slurry is now heated with stirring. The slurry canbe heated to evaporate the water which effectively impregnates thefluoride onto the pillars (impregnation method). Alternatively, theslurry is heated up to a temperature of about 60° C. to about 90° C. fora time of about 30 minutes to about 6 hours without evaporation of thewater (slurry method). If the water is not evaporated, the slurry isfiltered and the clay is washed with from about 5 liters to about 20liters of water. Regardless of whether the slurry or impregnation methodis used, the isolated clay is dried and then calcined at a temperatureof about 300° C. to about 600° C. for a time of about 1 hour to about 16hours. This process results in some or all of the hydroxyls on theoligomers being substituted with fluorides. The composition which isderived from this invention is useful as a catalyst or as a support formetals which are themselves catalysts. Thus, without any furthermodifications, the composition of this invention can be used to catalyzereactions such as alkylation, cracking, oligomerization, isomerizationand transalkylation. Additionally, a metal component (either as themetal or as the metal oxide) may be deposited on the composition toprovide additional or different catalytic properties. The metal whichmakes up the metal component may be selected from the group consistingof the Group IIIA, IIIB, IVB, VIII metals, molybdenum, tungsten andmixtures thereof.

The metal component may be deposited on the composition, which acts as asupport, in any suitable manner known in the art. One method involvesimpregnating the support with an aqueous solution of a decomposablecompound of the metal or metals. By decomposable is meant that uponheating the metal compound is converted to the metal or metal oxide andthe release of byproducts. Illustrative of the decomposable compounds ofsaid metals are cobalt chloride, cobalt nitrate, cobalt acetate, cobaltsulfate, iron chloride, iron nitrate, iron acetate, iron sulfate, nickelchloride, nickel nitrate, nickel acetate, nickel sulfate, ammoniumchloroplatinate, chloroplatinic acid, bromoplatinic acid, dinitrodiaminoplatinum, sodium tetranitroplatinate, rhodium trichloride,hexaamminerhodium chloride, rhodium carbonylchloride, sodiumhexanitrorhodate, chloropalladic acid, palladium chloride, palladiumnitrate, diamminepalladium hydroxide, tetraamminepalladium chloride,hexachloroiridate (IV) acid, hexachloroiridate (11I) acid, ammoniumhexachloroiridate (III), ammonium aquohexachloroiridate (IV), rutheniumtetrachloride, hexachlororuthenate, hexaammineruthenium chloride, osmiumtrichloride, ammonium osmium chloride, ammonium paramolybdate, ammoniumtungstate, aluminum chloride, aluminum nitrate, boric acid, galliumnitrate, gallium trichloride, indium chloride, indium nitrate, thalliumacetate, scandium nitrate, lanthanum chloride, lanthanum nitrate,yttrium chloride, yttrium nitrate, titanium trichloride, zirconiumtetrachloride, zirconium sulfate, and hafnium chloride. When more thanone metal is desired, the metals can be in a common aqueous solution orin separate aqueous solutions. When separate aqueous solutions are used,impregnation of the support can be performed sequentially in any order.Although the concentration of metal component can vary substantially itis desirable that the catalyst contain a concentration of the metalcomponent as the metal from about 0.1 to about 30 weight percent of thesupport and preferably from about 1 to about 15 weight percent. Apreferred impregnation procedure involves the use of a steam-jacketedrotary dryer. The support is immersed in the impregnating solutioncontaining the desired metal compound contained in the dryer and thesupport is tumbled therein by the rotating motion of the dryer.Evaporation of the solution in contact with the tumbling support isexpedited by applying steam to the dryer jacket. The resultant compositeis allowed to dry under ambient temperature conditions, or dried at atemperature of about 80° to about 110° C., followed by calcination at atemperature of about 400° to about 650° C. for a time of about 1 toabout 4 hours, thereby converting the metal compound to the metal ormetal oxide. As stated, the composition of this invention with orwithout an additional metal component can be used as an alkylationcatalyst. The conditions necessary to carry out alkylation of aromaticcompounds are well known and are disclosed, for example, in U.S. Pat.Nos. 3,965,043 and 3,979,331 which are incorporated by reference.Generally the process can be carried out in a batch type or a continuoustype operation. In a batch type process, the catalyst, aromatic compoundand alkylating agent are placed in an autoclave and the pressureincreased, if necessary, in order to effect the reaction in the liquidphase. An excess amount of aromatic compound should be present,preferably in a range of about 2:1 to about 20:1 moles of aromaticcompound per mole of alkylating agent. The reaction is carried out at anelevated temperature since the rate of alkylation is undesirably low atroom temperature. Preferably the temperature is in the range of about40° to about 200° C. The process is carried out for a time of about 0.5to about 4 hours, after which the product is separated from the startingmaterials by conventional means.

If it is desired to carry out the process in a continuous manner, thecatalyst is placed in a reactor which is heated to the desired operatingtemperature and the pressure increased above atmospheric, if necessary.The aromatic compound and alkylating agent are flowed over the catalystbed at a predetermined liquid hourly space velocity sufficient to effectalkylation. The effluent is continuously withdrawn and conventionalseparation means used to isolate the desired product.

Additionally, the composition of this invention with or withoutadditional catalytic metals or other catalytic materials such as Yzeolite may be used as a hydrocracking catalyst. Typically,hydrocracking conditions include a temperature in the range of 400° to1200° F. (204°-649° C.), preferably between 600° and 950° F. (316°-510°C.). Reaction pressures are in the range of atmospheric to about 3,500psig (24,132 kPa g), preferably between 200 and 3000 psig (1379-20,685kPa g). Contact times usually correspond to liquid hourly spacevelocities (LHSV) in the range of about 0.1 hr⁻¹ to 15hr⁻¹, preferablybetween about 0.2 and 3hr⁻¹. Hydrogen circulation rates are in the rangeof 1,000 to 50,000 standard cubic feet (scf) per barrel of charge(189-8,888 std. m^(3/) m³), preferably between 2,000 and 30,000 scf perbarrel of charge (355- 5333 std. m^(3/) m³).

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims.

EXAMPLE 1

In a 125 mL Parr Teflon Liner there were placed 4.8 g of Ce(NO₃)₃.6H₂ Odissolved in 66 g of aluminum chlorhydrate (ACH) sol (or 50 wt. %solution) obtained from Reheis. The liner was placed in a Parr Reactorwhich was placed in an oven heated to 135° C. After 5 days the reactorwas removed from the oven and the Ce-ACH isolated.

In a 3,000 mL, three neck round bottom flask equipped with a condenser,an overhead stirrer and a thermometer there were placed 2,100 g ofdeionized water and 137 g of Ce-ACH sol. The flask was heated to 95° C.and held there for 30 minutes, at which time 54 g of montmorilloniteclay (obtained from American Colloid and identified as HPM-20) was addedwhile stirring. The resultant slurry was heated at 95° C. for 1 hour atwhich time the clay was isolated by centrifugation. The clay was washeduntil chloride free and dried at 60° C. for 16 hours, followed bycalcination at 600° C. for 2 hours. The clay had a d₀₀₁ =26.5Å and aB.E.T. surface area of 550 m^(2/) g indicating that it was pillared.

EXAMPLE 2

In a container a slurry was prepared by adding 40 g of calcined Ce-ACHpillared montmorillonite clay prepared per Example 1 to 200 g of water.The slurry was heated to 85° C. in a constant temperature bath and then1.3 g of ammonium fluorosilicate (AFS) in 200 g of water was addeddropwise while stirring. After the AFS was added, the slurry was kept at85° C. for about 1 hour. The clay was next recovered by filtration,washed with 10 liters of deionized water and then calcined at 400° C.for 4 hours in a muffle oven.

EXAMPLE 3

In a container there were added 0.81 g of ammonium fluoride (NH₄ F) in20 g of water and 20 g of calcined Ce-ACH pillared montmorillonite clayprepared as in Example 1. The resultant slurry was stirred and the waterevaporated on a steam bath. The clay was then dried at 110° C. for 16hours and then calcined at 400° C. for 4 hours.

EXAMPLE 4

A fluorided pillared Ce-ACH montmorillonite clay was prepared as perExample 2 except that 1.69 g of ammonium fluoride was used as thefluoride source.

EXAMPLE 5

A fluorided pillared Ce-ACH montmorillonite clay was prepared as perExample 2 except that 0.34 g of ammonium fluoride was used as thefluoride source.

EXAMPLE 6

A fluorided pillared Ce-ACH montmorillonite clay was prepared as perExample 3 except that 1.63 g of ammonium fluoride in 20 g of water wasused.

EXAMPLE 7

The fluorided pillared Ce-ACH montmorillonite clays prepared in Examples3-6 as well as several other clays were tested using the followingheptene cracking test. The heptene cracking test uses an electricallyheated reactor which is loaded with 125 mg of 40-60 mesh (420-250microns) particles of the catalyst to be tested. The catalyst was driedin situ for 30 minutes at 200° C. using flowing hydrogen, and thensubjected to a reduction treatment of 425° C. in flowing hydrogen forone hour. The temperature of the reactor was then adjusted to 425° C.(inlet). The feed stream used to test the catalyst consists of hydrogengas which is saturated with 1-heptene at 0° C. and atmospheric pressure.The feed stream was flowed over the catalyst at a flow rate of 125cc/min. The effluent gas stream was analyzed using a gas chromatographin order to calculate weight percent cracked product. Cracked product isproduct that has a lower molecular weight than the starting 1-heptenehydrocarbon. The results of the heptene cracking test are presented inTable 2.

                  TABLE 2                                                         ______________________________________                                        Heptene Cracking Activity of Various Fluorided Ce-ACH                         Montmorillonite Clays.                                                        Fluoride                                                                              g Compound/           Cracking                                        Compound                                                                              20 g Clay   % Fluoride                                                                              Activity/ (% Conv)                              ______________________________________                                        **      **          **        3.7                                             AFS     1.30        1.49      25                                              AFS     2.60        2.92      61                                              NH.sub.4 F.HF                                                                         0.34        0.63      16                                              NH.sub.4 F                                                                            0.30        0.64      10                                              NH.sub.4 F                                                                            0.78        0.90      15                                               NH.sub.4 F*                                                                          0.81        2.30      39                                              NH.sub.4 F                                                                            1.69        1.60      26                                               NH.sub.4 F*                                                                          1.63        4.10      68                                              ______________________________________                                         *Impregnated                                                                  **Unfluorided CeACH montmorillonite                                      

The results presented in Table 2 show that activity is dependent on theamount of fluoride on the pillar.

EXAMPLE 8

This example presents the preparation of a fluorided pillared clay inwhich the clay is fluorided. First, to a solution consisting of 27 g ofNH₄ Cl in 500 g of deionized water, there were added 20 g ofmontmorillonite clay while vigorously stirring. The resultant slurry wasstirred for 2 hours at room temperature and then washed until thesupernatant is chloride free. Finally, the NH₄ -montmorillonite wasdried at 100° C. for 16 hours.

In a beaker there were mixed 10 g of the NH₄ -montmorillonite clayprepared above and a solution containing 5 g of NH₄ F and 100 gdeionized water. This slurry was placed in a Parr reactor and placed inan oven heated to 60° C. for 12 hours. The fluorided clay was recoveredby centrifugation and washed with 5 liters of deionized water.

The fluorided montmorillonite clay was pillared with Ce-ACH pillarsaccording to the procedure in Example 1. This clay was found to have 2.9wt. % fluoride. Finally, this clay was tested for heptene crackingactivity using the procedure of Example 7 and was found to have 12%cracking activity.

A comparison of this catalyst versus those of the invention shows thatfor the same amount of fluoride, the catalyst of this invention has 61%cracking. This indicates that fluoride is in different places on the twosamples.

I claim as my invention:
 1. A hydrocarbon conversion process comprisingcontacting a hydrocarbon feed under hydrocarbon conversion conditionswith a catalyst to give a hydroconverted product, the catalystcomprising a smectite clay having the empirical formula

    A.sup.n.sub.(x+z/n) (M.sub.8-x M1.sub.x)(M2.sub.(y-z) M3.sub.z)O.sub.20 (OH).sub.4

where A is a counter ion selected from the group consisting of alkalimetals, alkaline earth metals, secondary amines, tertiary amines,quaternary ammonium cations and quaternary phosphonium cations, n is thecharge on said counter ion, M is silicon or germanium, M1 is a metalhaving a +3 oxidation state selected from the group consisting ofaluminum, gallium, iron and chromium, x ranges from about 0 to about1.8, M2 is a metal having a +3 or a +2 oxidation state, M3 is a metalhaving a +2 or a +1 oxidation state, y is 4 when M2 is a +3 metal or 6when M2 is a +2 metal and z varies from about 0 to about 1.8, thesmectite clay having between its layers pillars which are metal fluorohydroxy polymer cations.
 2. The process of claim 1 where A is sodium, Mis silicon, M1 is aluminum, M2 is aluminum, z is 0 and the compositionhas the x-ray diffraction pattern of beidellite.
 3. The process of claim1 where A is sodium, M is silicon, x is 0, M2 is aluminum, M3 ismagnesium and the composition has the x-ray diffraction pattern ofmontmorillonite.
 4. The process of claim 1 where the metal in the metalfluoro hydroxy polymer cation is selected from the group consisting ofAl, Zr, Si/Al, Ti, and Cr.
 5. The process of claim 4 where the metal isaluminum.
 6. The process of claim 5 where the aluminum fluoro hydroxypolymer pillar is substituted with a rare earth metal.
 7. The process ofclaim 6 where the rare earth metal is cerium.
 8. The process of claim 1where the hydrocarbon conversion process is alkylation.
 9. The processof claim 1 where the hydrocarbon conversion process is hydrocracking.